Polymerizable crosslinkable esters of polyepoxy compounds

ABSTRACT

Crosslinkable derivatives containing acrylic ester linkages are prepared by the reaction of a polyepoxide (compounds having a plurality of GROUPS) WITH AN ACRYLIC ANHYDRIDE OF A MONOCARBOXYLIC ACID, CH2=C(Y)COOOCR&#39;&#39;. The derivatives are crosslinked readily by ultraviolet light and ionizing radiations as well as by chemical initiators, and can be used for the preparation of homopolymers and copolymers. They find utility as casting, potting, laminating and molding compounds, as coatings and impregnants, electrical insulators and the like.

United States Patent DAlelio [451 July 11, 1972 [54] POLYMERIZABLECROSSLINKABLE ESTERS OF POLYEPOXY COMPOUNDS [72] Inventor: Oaetano F.DAlelio, South Bend, Ind.

[73] Assignee: PPG Industries, Inc., Pittsburgh, Pa.

[22] Filed: Nov. 25, 1968 :1 Appl. No.: 778,825

[5 6] References Cited OTHER PUBLICATIONS Journal of Organic ChemistryJ. Smith, Jr. et al. I/ 1961 (pp. 1,283- 1,284) 13) I Handbook of EpoxyResins Lee et a1. 7/1967 (pp. 5- 32; 12-

13) Preparative Methods of Polymer Chemistry Sorenson et a1. 1961 (pp.286; 287) Primary Examiner-William 11. Short Assistant Examiner-T.Pertilla AttarneyRussell A. Eberly 57 ABSTRACT Crosslinkable derivativescontaining acrylic ester linkages are prepared by the reaction of apolyepoxide (compounds having a plurality of C! (I:

groups) with an acrylic anhydride of a monocarboxylic acid,

CH C(Y)COOOCR. The derivatives are crosslinked readily by ultravioletlight and ionizing radiations as well as by chemical initiators, and canbe used for the preparation of homopolymers and copolymers. They findutility as casting, potting, laminating and molding compounds, ascoatings and impregnants, electrical insulators and the like.

21 Claims, No Drawings POLYMERIZABLE CROSSLINKABLE ESTERS OF POLYEPOXYCOMPOUNDS This invention relates to polymerizable monomers as theproducts of reaction of polyepoxides with acryloyl carboxylic acidanhydrides and to the polymers derived from such monomers. The termpolyepoxide" refers to compounds containing two or more epoxide" orepoxy groups; and the term epoxide" or epoxy" refers to the oxiranegroup,

More particularly, it deals with the reaction product of a polye'poxidecontaining at least two epoxy groups,

in its structure with an acryloyl carboxylic acid anhydride of theformula The reaction of the epoxy groups in the polyepoxides with theseanhydrides yields the diester derivatives,

Accordingly, the monomeric reaction product contains at least two groupsrepresented by structure (A), in which Y represents H, CH Cl, Br, andCN; R represents H, a group which is essentially hydrocarbon containingone to 20 carbon atoms, and a halogenated derivative of the saidhydrocarbon group.

The only requirement of the polyepoxide used in the reaction is that itcontains at least two wherein Q is the organic residue of a polyepoxide;R" represents hydrogen and a lower hydrocarbon group containing one to10 carbon atoms, preferably hydrogen; n has a numerical value of atleast 2 and may be as high as 100 or more. represents any of alargenumber of organic structures to which the epoxy group can beattached directly, or indirectly through heteroatoms such as O, S, N, P,etc., and Q can be a hydrocarbon structure consisting solely of carbonand hydrogen or a structure containing, in addition to carbon andhydrogen, atoms of nitrogen, silicon, phosphorus, or oxygen, etc.,numerous examples of which are given hereinafter.

The acryloyl carboxylic acid anhydrides used in the practice of thisinvention are conveniently prepared by the metathesis of an acyl halideand an alkali metal carboxylate by procedures given in the Journal ofOrga nic Chemistry, Vol. 26, p. 1283 (196i according to the equationRCOCl ltUOONn -b NziCl RCOOCR (Eq. 1)

(JIIaCIIzCOOK ()IIFCIICOCI ClIaCHzCOOOCII=CIIz ()I'IaCHzCOClCIIFCIICOONa CIIaCHzC OOOCCH=CII2 The boiling point of CH CH CHOOOCCH CHis 32 C. at 0.5 mm; that of CH C(CH )COOOCHC CH is 64 C. at 4.0 mm; thatof CH CHCOOOCHC CH is 21 C. at 0.2 mm; and that of CH C(CH )COOOCC(CH CHis 32 C. at 0.5 mm Hg pressure. High boiling acryloyl anhydrides, suchas those in which R contains five or more carbon atoms or a plurality ofhalogen atoms tend to dispropor- While a minor amount ofdisproportionation is not serious to the practice of this invention,such mixtures are undesirable and, accordingly, such anhydrides arepreferably used without distillation, either in the non-reactivesolvents in which they are prepared, or, after removal of the solvent atreduced pressures. The acyl halide and alkali metal carboxylate used inthe syntheses of the non-distilled acryloyl carboxylic anhydrides shouldbe of high purity. Also, the undistilled solutions of these anhydrides,which used, are preferably purified by treatment with activated carbonsor silica-type absorbents.

Typical examples of acryloyl carboxylic acid anhydrides useful in thepractice of this invention are those acryloyl anhydrides, CH CHCOOOCR',CH C(CHQCOOOCR', CH C(CN)COOOCR', CH C(C1)COOOCR', CH C(Br)COOOCR', inwhich the acryloyl groups are derived from the acrylic acids, CH CHCOOH,CH C(CHQCOOH, CH C(CN)COOH, CH C(Cl)COOH and CH C(Br)COOl-l. Their acylhalides, CH C(Y)COX, or their alkali metal salts, CH C(Y)COOM, where Mrepresents an alkali metal, may be used in the syntheses as given inequation 1 hereinabove, by reaction with the acylhalides, R'COCI, or thealkali metal salts, RCOOM, derivable from RCOOH acids.

Various hydrocarbon groups represented by R in the R'COO-formula includealiphatic, cycloaliphatic and aromatic hydrocarbon radicals such asmethyl, ethyl, propyl, butyl, amyl, hexyl, octyl, nonyl, dodecyl,octadecyl, cyclohexyl, cycloheptyl, phenyl, tolyl, xylyl, naphthyl,diphenyl, methylcyclohexyl, ethylcycloheptyl, cycloheptylpropyl,phenethyl, ethylphenyl, butylnaphthyl, octyldiphenyl, butenyl, octenyl,phenylbutenyl, styryl, cyclohexylpropenyl, etc. While acetylenic, spiroand various other less common types of hydrocarbon groups can also beused these are more expensive and less practical for the purpose of thisinvention.

Typical preferred acyloxy groups include, in addition to the acryloxyand OOCR- groups, acetoxy, formyloxy, propionoxy, benzoxy, phenylacetoxyand butyroxy.

Other examples of RCOOl-l acids are the CH C(Y)COOH acids, such as CHCHCOOH, CH C(CH )COOH, CH C(CN)COOl-l, CH C(Cl)COOH, CH C(Br)COOI-l,HCOOH, CH COOl-l, C H COOH, C H,COOH, C l-l COOl-l, C H COOH, C H COOH,C l-l COOl-l, C l-L CO0H, cl CCOOl-l, Br CCOOl-l, Cl CHCOOH, CICH COOH,cn cn CHCOOH, HC CCOOl-l, ClC CCOOl-l, BrC CCOOl-l, Br C CBr- HOOCC (ClCOOCH- CH CH HOOC (CI).,COOCH CH OOCCH CH l-lOOCCl-l P(O)(OCl-l )2,HOOCCH P(O)(OCHCl-l CH HOOCCH CH C ON(CH etc. Where the R group in theseacids is not completely hydrocarbon by virtue of the presence of amethoxy, hydroxy or other group as shown, these are considered asequivalent to hydrocarbon for the purpose of this invention.

Any of the known polyepoxides may be reacted with the above acryloylcarboxylic acid anhydride to form the curable products of thisinvention.

Useful polyepoxides are the glycidyl ethers of both polyhydric phenolsand polyhydric alcohols, epoxidized fatty acids or drying oil acids,epoxidized diolefins, epoxidized diunsaturated acid esters, as well asepoxidized unsaturated polyesters, preferably containing more than oneepoxide group per molecule.

Glycidyl polyethers of polyhydric phenols are made from the reaction ofa polyhydric phenol with epihalohydrin or glycerol dihalohydrin, and asufficient amount of caustic alkali to combine with the halogen of thehalohydrin. The preparation of these polyepoxides is described morefully in U.S. Pat. Nos. 2,467,171, 2,538,072, 2,582,985, 2,616,007 and2,698,315.

Glycidyl ethers of polyhydric alcohols are made by reacting at leastabout two moles of an epihalohydrin with one mole of a polyhydricalcohol such as ethylene glycol, pentaerythritol, etc., followed bydehydrohalogenation according to U.S. Pat. No. 2,581,464.

In addition to polyepoxides made from alcohols or phenols and anepihalohydrin, polyepoxides made by the known peracid methods are alsosuitable. Epoxides of unsaturated esters, polyesters, dioleflns and thelike can be prepared by reacting the unsaturated compound with aperacid. Preparation of polyepoxides by the peracid method is describedin various periodicals and patents and such compounds as butadiene,ethyl linoleate, as well as dior tri-unsaturated drying oils or dryingoil acids, esters and polyesters can all be converted to polyepoxides.

Epoxidized drying oils are also well known, these polyepoxides usuallybeing prepared by reaction of a peracid such as peracetic acid orperformic acid with the unsaturated drying oil according to U.S. Pat.No. 2,569,502.

Desirable esters are prepared by reacting unsaturated aldehydes withbutadiene to form unsaturated cyclic aldehydes. These can be condensedby the Tischenko reaction to form esters or reduced to form alcoholswhich can subsequently be reacted with acids to form esters. In additionto epoxidized drying oils, butadiene dioxide and monomeric esters,polymeric esters can also be epoxidized by the peracid method asdescribed in Australian Pat. No. 1 1,862 (1955). Examples of theseunsaturated polyesters are those made from saturated polyhydric alcoholsand unsaturated polybasic acids, for example, maleic acid, 2-butenedioicacid, 4-cyclohexene-l,2- dicarboxylic acid, dimerized linoleic acid,etc., and such alcohols as ethylene glycol, 1,6-hexanediol,3-ethylhexanediol- 1,3-pentaerythritol, etc. Other polyesters which canbe epoxidized with peracetic or other peracids are made from saturatedacids and unsaturated alcohols, for example, 2-butenedioll ,4;l,5-hexanediene-3,4-diol; 2-pentene-1,5-diol; cyclohexenediol-2,5ol;etc. reacted with such saturated acids or acid anhydrides as malonic,succinic, glutaric, terephthalic,

BIC.

Examples of such polyepoxides include diglycidyl ether, the diglycidylether of diethylene glycol or dipropylene glycol, the diglycidyl etherof polypropylene glycols having molecular weight up to, for example,about 2,000, the triglycidyl ether of glycerine, the diglycidyl ether ofresorcinol, the diglycidyl ether of 4,4'-isopropylidene diphenol, epoxynovolacs, such as the condensation product of 4,4-methylenediphenol andepichlorohydrin and the condensation of 4,4-isopropylidenediphenol andepichlorohydrin, glycidyl ethers of Cashew nut oil, epoxidized soybeanoil, epoxidized unsaturated polyesters, vinyl cyclohexene dioxide,dicyclopentadiene dioxide, dipentene dioxide, epoxidized polybutadieneand epoxidized aldehyde condensates such as 3,4-epoxy-6-methylcyclohexylmethyl, 3,4-epoxy-6-methylcyclohexane carboxylate (Unox201 Additional examples of useful polyepoxides are given in U.S. Pat.No. 3,379,653.

The reaction between the polyepoxide and the acryloyl-carboxylic acidanhydride can be performed over a wide range of temperatures from 10 to150 C., preferably 50 to C. in the absence or presence of solvent atatmospheric, sub-atmospheric or superatmospheric pressure; preferably inan inert atmosphere. To prevent premature or undesirable polymerizationof the derived diester it is advantageous to add a vinyl inhibitor tothe reaction mixture. Suitable vinyl polymerization inhibitors includetert-butylcatechol, hydroquinone, 2,5-ditertiarybutylhydroquinone,hydroquinonemonoethyl ether, etc. Advantageously, the inhibitor isincluded in the reaction mixture at a concentration of about 0.005 to0.1 percent by weight based on the total of the reagents.

The reaction between the polyepoxide and the acryloylcarboxylic acidanhydride proceeds slowly when uncatalyzed, and can be accelerated bysuitable catalysts which preferably are used, such as, for example, thetertiary bases such as trimethyl amine, tributylamide, pyridine,dimethylaniline,

N(CH CH )C3N, tris(dimethylaminomethyl)-phenol, triphenylphosphine,tributyl phosphine, tributylstilbine; the alcoholates such as sodiummethylate, sodium butylate, sodium methoxyglycolate, etc.; thequarternary compounds such as tetramethylammonium bromide,tetramethylammonium chloride, benzyl-trimethylammonium chloride, and thelike. At least 0.01 percent, based on total weight of reagents,preferably at least 0.1 percent of such catalyst is desirable.

The reactions between the CH C(R)COOOCR and the polyepoxide can beperformed in the presence of suitable organic solvents, which do notreact with either the above anhydrides or the polyepoxides, especiallythe ethers, the esters, the ketones and the hydrocarbon solvents, suchas diethyl ether, ethyl acetate, acetone, methyl propyl ketone,cyclohexane, benzene, toluene, tetrahydrofuran, dioxane and the like. Inmost cases, it is preferred to perform the reaction so that thecrosslinkable diester derivative can be isolated directly and used assuch or admixed with other polymerizable monomers or polymers. 1f thederived crosslinkable diester derivative is desired to be mixed withother monomers, the reaction can be performed in the presence of suchmonomers.

Typical examples of suitable monomers which can be used and added to thereaction mixture before or during the reaction, or added after thereaction are the vinyl or vinylidene monomers containing ethylenicunsaturation,

and which can copolymerized with the crosslinkable diester derivativesof this invention are, styrene, vinyl toluene, tertiary butyl styrene,alpha-methyl-styrene, monochlorostyrene,

dichlorostyrene, divinylbenzene, ethyl vinyl benzene, diisopropenylbenzene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethylmethacrylate, acrylonitrile,

methacrylonitrile, the vinyl esters, such as vinyl acetate and themonovinyl esters of saturated and unsaturated aliphatic, monobasic andpolybasic acids, such as the vinyl esters of the following acids:propionic, isobutyric, caproic, oleic, stearic, acrylic, methacrylic,crotonic, succinic, maleic, fumaric, itaconic, hexahydrobenzoic, citric,tartaric, etc., as well as the corresponding allyl, methallyl, etc.,esters of the aforementioned acids, the itaconic acid monoesters anddiesters, such as the methyl, ethyl, butyl esters, etc.; the maleic andfumaric acid monoesters, diesters and their amide and nitrile compounds,such as diethyl maleate, maleyl tetramethyl diamide, fumaryl dinitrile,dimethyl fumarate; cyanuric acid derivatives having at least onecopolymerizable unsaturated group attached directly or indirectly to thetriazine ring such as diallyl ethyl cyanurate, triallyl cyanurate, etc.;ethers such as vinyl allyl ether, divinyl ether, diallyl ether,resorcinol divinyl ether, etc., diallyl chlorendate, diallyl tetrachlorophthalate, diallyl tetrabromophthalate, dibromopropargyl acrylate, aswell as the partial fusible or soluble polymerizable polymers of thehereinabove listed monomers, etc.

in preparing the interpolymerization products of the crosslinkablederivatives of this invention, and one or more of the modifying monomerof the type listed hereinabove, the modifying monomers can constitute asmuch as 98 to 99 percent by weight of the whole, whereas in other casesthe modifying monomers can constitute as little as l to 2 percent byweight of the whole. In general, however, the modifying monomer ormonomers are used in the range of to 80 percent by weight of the whole.

The new crosslinkable derivatives of this invention can be used also tomodify other polymers such as polyvinylacetate, polymethylmethacrylate,cellulose acetate, cellulose butyrate, ethyl cellulose, polyethyleneadipate, polydecamethylene sebacate, polystyrene, polyvinyl chloride,poly-(vinyl chloride-vinyl acetate) copolymers, polyethylene adipamide,polycaprolactam, etc. The new crosslinkable derivatives of thisinvention are especially useful for modifying polymers containingunsaturated vinyl or vinylidene groups with which they copolymerizereadily, such as the natural and synthetic polydienes commonly known asrubbers; partially polymerized fusible, soluble polyallyl esters such asdiallyl phthalate, diallyl succinate; linear polymers of allyl acrylate,allyl methacrylate, p-alIyloxy-styrene, etc. and particularly theunsaturated alkyd resins, which are well known in the art, such as themaleic, fumaric, itaconic acid esters of polyhydric alcohols which canbe modified by other monoand polycarboxylic acids, for example,-ethylene glycol-maleate, ethylene glycol-maleate-phthalate, propyleneglycolmaleate phthalate, propylene glycol-fumarate phthalate,di-(hydroxyethoxy)phenyl-fumarate, di(hydroxypropoxy)phenyl-fumarate,etc.

The new derivatives of this invention can be cured or converted to theinfusible state, alone or in admixture with other monomers or polymersthermally by the application of heat alone or in the presence of radicalgenerating catalysts such as the peroxyand azotype initiators such asazobisisobutyronitrile, benzoyl peroxide, tertiary butyl peroxide,lauroyl peroxide, tertiary butyl peracetate, tertiary butyl perbenzoate,acetyl peroxide, hydrogen peroxide alone or in the presence of a redoxagent such as sulfurous acid, the persulfates alone or in the presenceof redox agents such as the bisulfites, ferrous compounds, etc.;ultraviolet light and ionizing radiation such as generated by X-Raymachines, electron accelerators such as van der Graaf machines,travelling wave linear accelerators, particularly of the type describedin US. Pat. No. 2,736,609, natural and synthetic radioactive material,for example cobalt 60, etc.

The compositions of this invention are useful in the preparation ofmolded, cast, laminated and coated products as adhesives, impregnantsand protective coatings. They can be used alone or with fillers, dyes,pigments, opacifiers, lubricants, plasticizers, natural or syntheticresins or other modifying bodies.

In coating, impregnating and similar applications, the compositions,without added solvent, can be applied to the object to be treated andpolymerized, with or without the application of heat and pressure, toform the final insoluble polymeric composition in situ. These newsynthetic materials can be used as impregnants for many porous bodies,such as cork, pottery, felts, or fabricated bodies with interstices,such as the windings of electrical coils, netted fibers, interwovencotton or glass materials, etc. They can also be used for the productionof wire coatings and winding tapes, and for protectively coatingimpervious articles, such as metals, or for coating and impregnatingarticles such as paper, wood cloth, glass fibers in felted, woven orother form, concrete, linoleum, synthetic boards, etc. These newsynthetic materials can also be employed in making laminated fibroussheet materials wherein superimposed layers of cloth, paper, glassfabrics or mats, etc., are firmly bonded together with these newcompositions.

For coating or impregnating applications where the presence of a smallamount of solvent in the cured composition is not objectionable, themixed starting component can be diluted with volatile or nonvolatilesolvents or diluents best suited for the particular service application,and then can be polymerized after the application of the solution to theparticular article to be coated or impregnated, or impregnated andcoated. By suitable selection of the starting material and theconditions of the interpolymerization, interpolymers can be obtained inan insoluble, infusible state practically resistant to the destructiveefiect of other chemical bodies, such as acid, bases, salts, solvents,welling agents, and the like.

The polymeric compositions of this invention are particularly useful ascoating compositions on all types of substrates,

including cellulose in its various forms, such as paper, wood,'

paper board, wood board, wood pulp, regenerated cellulose in film orfiber form, laminates of various types including those prepared fromfibrous fillers bonded with urea, melamine, epoxy and polyester resins,plaster board, concrete in its various forms such as slabs, blocks andthe like. They may also be used as impregnants for porous bodies such asthe compositions hereinable named, as well as for synthetic and naturalsponges, etc. Particularly do they find use as bonding agents andadhesives for solid, porous and foamed bodies.

Various methods of practicing the invention are illustrated by thefollowing examples. These examples are intended merely to illustrate theinvention and not in any sense, to limit the scope of the invention orthe manner in which it can be practiced. The parts and percentagesrecited therein and throughout this specification, unless specificallyprovided otherwise, refer to parts by weight and percentages by weight.

EXAMPLE I A mixture of 146 parts of a vinylcyclohexenediepoxide, C H Oepoxy resin having an epoxy equivalent of 73, 114 parts of CH CHCOOOCCH2 parts of triethylamide and 0.15 part of hydroquinone are reacted withstirring under a nitrogen atmosphere at 75 C. for l hour and then at C.for 3 hours or until the acid number drops below 6 and there is obtainedan almost quantitative yield of /on, F o CIICI-I CIIz=ClICOO i IiOOCCH=CIIz c a 000 000011 11; g /o1-n om-J 3 This is a viscous oilwhich on analysis gives values of 68.50 percent C and 8.59 percent H.These values are in good agreement with the calculated values for thecompound.

EXAMPLE II The procedure of Example I is repeated a number of times,using, with the vinylcyclohexenedieposide, instead of the acetylacrylicanhydride, other anhydrides of the formula, CH C(Y )COOOCR', shown inTable 1, so that two ester pairs are attached to the vinyl-cyclohexanenucleus corresponding to the same groups in the anhydride, instead ofthe ester pairs shown in Example I.

TABLE 1 TABLE 1 Cominued Reactions 0f CH2=C(Y)COOOCR withvinylcyclohexenediepoxide H "CHTJCHCOOCHZ XXI Derivative CH2=CHCOO Hz IY E R group um CH=CHCOOCHCHQ XXII I EH: Ha- III CH2=(CH3) CO 0 CH2 ItEEZZEI T H CH2CH:C0N(CH:)2 XXIII (uhc1 ;(;1 v1 H- CH2) CHzCOOCH: XXIV(1Ih, Cl%2- G(CII:) (}I- CI 1 mour- 10 EXAMPLE H1 ON 011,- n-

cm XI The procedure of Example I Is repeated usmg CH EI' CHCOOOCH; andinstead of vinylcyclohexenediepoxide, CH III. CaBrr-H X9 equivalentweights of the diepoxides shown in Table 2 and the H-" c o X XVI 5acetyl acrylyl ester denvatlves, H -CBr:CHBr XVII H CH2OC1I3 XVIIIOOCHC=CH2 H CH2CH:COOC2HI XIX 000cm H- M CH=CHCOOCH1 XX CHFCHcorresponding to the diepoxides used are obtained.

TABLE 2 Reactions of CH2=CHCOOOCCH3 with various diepoxidee Dlepoxideused fixa CHz-CH-CH/CH2 XXV XXVI -CH2OOC O O XXVII CHzCHCHzO- OCHzOHCHzO CH:

TABLE 2 Continued Reactions of CH2=CHCOOOCCH3 withvnrious diopoxidesDiepoxide used i (i'lHa XXXV CH-C o 0CHz(|3H'CHzO O -p-@-o 0111011011:

OH CH:

(IT/Ha 011-0 0 o OHzCIJHCHzO@-(IJ@O 0112011011,

' OH CH; 0

0 v xxxvi O C CHCHz/CH--CH1 CH: N-CH: CH: CE:

I I i CHCH 1%I-CH2 i I OCHOH ;CH--CH2 0g: /CH

CHCH

COOCHzCHCHz XXXVII (Br)l'lo 0 0 0 CHZCHCH:

H5021 (O) (NHCOOCHzCHCI-h): XXXVIII EXAMPLE lV polyepoxides, thederivative contains in addition to two ester derivative functions,

The procedure of Example I is repeated, instead of thevinylcyclohexenediepoxide, polyepoxides shown in Table 3 having morethan two epoxy groups with at least two OOCCH CH less than theequivalent number of epoxy groups in the sites.

unconverted oxirane groups which can function as bonding TABLE 3Reactions oi CH1=CHCOOOCCH with various plyepoxides Polyepoxides usedEquivalents oi CII CHCOOOCCI-I: Derivative used number Same as aboveCHnCHCH: O O

2 XXXIX XLI TABLE 3 Continued Reactions of CHz=CHCOOOCCH with variousplyopoxldos Equivalents ol' CHg=CHCOOOCCIIs Dt'rlvntlvo Polyepoxldesused used number C(CHzOCHzCHCH2)4 4 XLII Same as above 3 XLIII OCH1CHCH13 XLIV O HaC- -CH:

OCH:CHCH1 HaC- CHz I O CHrCHCH;

Poly CHzOH l XLV OOCHzCHCHI Same as above 1 100 XLVI Do l XLVII orroH,oni-o 012m 011,011] 1 4 XLVIII l 5L J50 a 00911; OOCH; COOCIH: CH CE 1H2 Same as above 1 10 XLIX 1 In 1,000 parts dioxane.

EXAMPLE v EXAMPLE VII The reaction, according to the procedure ofExample I, of the anhydrides, respectively, of Example II with each ofthe polyepoxides used in the synthesis of derivatives numbers XX- Vlll,XXXII, XXXIII, XXXV, XXXVI and XXXIX yield the polymerizable derivativescorresponding to the nuclei of the polyepoxide used to which is attachedester groups derived from the specific anhydride used.

EXAMPLE VI a. The procedure of Example III is repeated but the reactionis performed in the presence of parts of styrene for each 50 parts ofderivative to be obtained and there results a polymerizable solution ofthe derivative in the styrene monomer.

. The ratio of styrene to derivative is modified by varying the amountof styrene used to obtain ratios to the derivative of 1:99 to 99:1 assolutions containing the crosslinkable copolymerizable components.

c. The substitution of styrene in Examples VI(a) and VI(b) by methylmethacrylate, vinylacetate, diallyl phthalate, glycol dimethacrylate,acrylic acid, glycidyl acrylate and hydroxyethylacrylate yieldspolymerizable solutions containing the derivatives dissolved in therespective monomers.

EXAMPLE VIII To each of the derivatives I, IV, VII, XI, XIV and XXI isadded 0.01 percent by weight of benzophenone, and the mixture exposed tothe ultraviolet light from a 20 ampere carbon arc lamp for 4 minutes,and insoluble, infusible polymers are obtained in all cases. Theinsoluble product from XIV is selfextinguishing.

EXAMPLE IX To a mixture of 50 percent by weight of a derivative I and 50percent glycol-fumarate-phthalate is added 0.1 percent by weight oftertiary butyl hydroperoxide and 0.05 percent by weight of cobaltnaphthenate and, on standing for hours at EXAMPLE X Samples of each ofthe derivatives I, IV, VII, XX, XXI, XXII, XXVlll, XXXl, XXXII and XXXVare exposed to the beam of a l MEV van der Graaf accelerator and in allcases the samples become crosslinked and infusible at radiation dosagesof less than 5 megarads.

EXAMPLE XI The procedure of Example X is repeated after first mixing-the derivatives I, IV, VII, XX, XXI, XXII, XXVIIL'XXXI,

XXXII and XXXV with methyl methacrylate in ratios by weight of 95:5,50:50 and 5:95 and in all cases crosslinked polymers are obtained.

EXAMPLE Xll To 75 parts of derivative XXVIII is added 25 parts ofstyrene, 40 parts of calcium carbonate as a filler and 1 part oftertiary butyl perbenzoate and the mixture blended to uniformity. Themixture is applied to glass-fiber mats (1.5 ounces of glass per squarefoot of mat surface) so that the glass comprises about 40 percent of thecomposition. Five glass mats are arranged one-atop-another as afive-layer laminate assembly and cured between the heated plates of amold for l0-l5 minutes at 130 C. at 150 psi. The flexural strength ofthe laminate, as prepared, is in the range of 30,000 to 33,000 psi andthe tensile strength in the range of 17,000 to 19,000 psi.

EXAMPLE XIII A solution is prepared from 100 parts of derivative XL, 100parts of diallyl phthalate, 100 parts of toluene, 50 parts of ethylalcohol and 2 parts of dicumyl peroxide. The solution is applied as acoating to multifilament glass threads by drawing the fibers through thesolution, and is then dried to evaporate the toluene and alcohol. Thedried impregnated thread is then used for the production of spiral woundfilament forms and the formed structure cured at 130 C. for 2 hours,followed by postcuring at 180 C. for 50 hours.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention and it is not intended to limit the invention tothe exact details shown above except insofar as they are defined in thefollowing claims.

The invention claimed is:

l. A process for producing a soluble, crosslinkable product comprisingthe step of reacting in the presence of a vinyl polymerization inhibitorand an inert atmosphere a. a polyepoxide having a plurality of epoxidegroups of the formula with b. an anhydride of the formula CI-lC(Y)COOOCR wherein Y is a member selected from the class consisting ofH, CH Cl, Br and CN; R is selected from the class consisting of H, ahydrocarbon group of one to 20 carbon atoms, and halogenated derivativesof said group; and R" is selected from the class consisting of hydrogenand a hydrocarbon radical of one to carbon atoms.

2. The process of claim 1 in which at least two equivalents of CH,C(Y)COOOCR are reacted per polyepoxide molecule.

3. A product having the formula LL l J wherein n has a numberical valueof at least 2 and Q is the residual organic moiety of the polyepoxidewherein Y is a member selected from the class consisting of H, CH Cl. Brand CN; R" is selected from the class consisting of H, a hydrocarbongroup of one to 20 carbon atoms and halogenated derivatives of saidgroup; and R is selected from the class consisting of hydrogen and ahydrocarbon radical of one to l0 carbon atoms.

4. A therrnoset polymer comprising the polymerization product of claim3.

5. The process of claim 2 in which the polyepoxide is (Phil-$3112 |C11II: (I) O O O CH: I

l l RI! n III wherein n has a numerical value of one to 10, and R"represents hydrogen or a lower hydrocarbon radical of one to six carbonatoms.

6. The process of claim 2 in which the polyepoxide is wherein n is aninteger having a value of 0 to 10.

7. The process of claim 2 in which the polyepoxide isvinylcyclohexenediepoxide.

8. The process of claim 2 in which the polyepoxide is in which Ar is anarylene group containing six to 12 carbon atoms.

9. The process of claim 2 in which the anhydride is I CH2=CCOOOCCH3 10.The process of claim 2 in which the anhydride is i CHz=C C O O O C QaXswhere X represents Cl and Br.

11. The process of claim 8 in which Y is H.

12. The process of claim 9 in which Y is H.

13. The process of claim 2 which comprises 5 to percent by weight of atleast one copolymerizable monomer having at least one terminal group.

14. A compound having the formula in which Y is a radical selected fromthe class consisting of H, CH Cl, Br and CN; and R is selected from theclass consisting of H, a hydrocarbon group of one to carbon atoms, andthe halogenated derivatives of said hydrocarbon groups 18. The thermosetpolymerized product of a polymerizable mass comprising 5 to percent byweight of the compound of claim 16.

19 The thermoset polymerized product of a polymerizable mass comprising5 to 95 percent by weight of the compound of claim 17.

20. The process of claim 1 which comprises performing the reaction inthe temperature range of 10 to C. in the presence of at least 0.01percent by weight of a tertiary base.

21. The process of claim 20 in which the reaction is performed in thepresence of 5 to 95 percent by weight of at least one copolymerizablemonomer containing at least one terminal group.

2. The process of claim 1 in which at least two equivalents ofCH2=C(Y)COOOCR are reacted per polyepoxide molecule.
 3. A product havingthe formula wherein n has a numberical value of at least 2 and Q is theresidual organic moiety of the polyepoxide wherein Y is a memberselected from the class consisting of H, CH3, Cl, Br and CN; R'''' isselected from the class consisting of H, a hydrocarbon group of one to20 carbon atoms and halogenated derivatives of said group; and R'''' isselected from the class consisting of hydrogen and a hydrocarbon radicalof one to 10 carbon atoms.
 4. A thermoset polymer comprising thepolymerization product of claim
 3. 5. The process of claim 2 in whichthe polyepoxide is
 6. The process of claim 2 in which the polyepoxide iswherein n is an integer having a value of 0 to
 10. 7. The process ofclaim 2 in which the polyepoxide is vinylcyclohexenediepoxide.
 8. Theprocess of claim 2 in which the polyepoxide is in which Ar is an arylenegroup containing six to 12 carbon atoms.
 9. The process of claim 2 inwhich the anhydride is
 10. The process of claim 2 in which the anhydrideis where X represents Cl and Br.
 11. The process of claim 8 in which Yis H.
 12. The process of claim 9 in which Y is H.
 13. The process ofclaim 2 which comprises 5 to 95 percent by weight of at least onecopolymerizable monomer having at least one terminal group.
 14. Acompound having the formula
 15. A compound having the formula
 16. Thecompound of claim 14 in which R'' is CH3.
 17. The compound of claim 15in which R'' is CH3.
 18. The thermoset polymerized product of apolymerizable mass comprising 5 to 95 percent by weight of the compoundof claim
 16. 19. The thermoset polymerized product of a polymerizablemass comprising 5 to 95 percent by weight of the compound of claim 17.20. The process of claim 1 which comprises performing the reaction inthe temperature range of 10* to 110* C. in the presence of at least 0.01percent by weight of a tertiary base.
 21. The process of claim 20 inwhich the reaction is performed in the presence of 5 to 95 percent byweight of at least one copolymerizable monomer containing at least oneterminal group.